Alcohol hydrofinishing



July 5, 1960 E. w. NMMENsEN ETAL 2,944,087

ALCOHOL HYDROFINISHING 3 Sheets-Sheet 1 Filed May 1e, 1955 T@ I esta N: 4 Il WUIIUIMWMM livnHuvMMWWU a 4 2x Al EEE QT /1 25 sa s, x A a 1 ,s Il h1 N l s m n m M m .m T A AI m m mur/h/HHhmlwm m WIJ... nhunvfwwnu Al MM n mwmm E WH Mfc ms WA. K.T. I D HE I m0" Wm V! f) .as lm: n EE@ July 5, 1960 E. w. NoMMENsEN AEl-Al. 2,944,087

ALCOHOL HYDROF INISH ING Filed May 16, 1955 3 Sheets-Sheet 2 f :I 0.l00 1 o l I l i D 5 l0 l5 FEED RATE. LIQUID V/ V/HR.

ETHANOL HYDRDFINISHNG LABDRATDRY DDNTINUDUS UNIT RELATIONSHIP BETWEEN NDI. INCREASE AND LIOUID FEED RATE "0000" JosEPH K.' MfRrzwf/LLER INVENTORS ELA/NE r. 0501005 BY KMA/7 M ATTORNEY July 5, 1960 E. w. NoMMENsEN ETAL 2,944,087

ALCOHOL HYDROFINISHING Filed May 16, 1955 3 Sheets-Sheet 5 A HDI. (PRODUCT HDL-FEED HDI.)

6D 80 T00 120 M0 i60 180 TE HR, "E

EFFECT 0F TEMPERATURE 0N M.0.l. l0 V/ V/HR., 0 RSLGJD SGF HYDRDGEN l BBL. FEED A N.0.l. (PRODUCT N.0.l. MINUS FEED H.0.I. VERSUS TEMP. E

ERWIN W. NDMHENSER gow/mo A, HUNTER JOSEPH K. MERrZv/HLLER INVENTORS ELAINE T. DELAUNE BY ATTDRNE Y ALCGHGL HYDROFINISHING Erwin Ward Nommensen, Edward Allen Hunter, Joseph Kern Mertzweiller and Elaine Theodora Delaune, Baton Rouge, La., assignors to Esso Research and Engineering Company, a corporation of Delaware Filed May 16, 1955, Ser. N0. 508,604

3 Claims. (Cl. 260643) This :invention relates to a method of using a mild hydrogenation on slightly impure ethanol, particularly, ethanol synthesized by ethylene hydration and puriiied by water extractive distillation, for obtaining a iual purification.

It is known .that in 'the'past methods of refining impune ethyl alcohol or ethanol by hydrogenation have been proposed. VGenerally, these past methods including hydrogenation for other catalytic treatment were imposed on lth'e orudealcohol containing relatively substantial amounts or impurities and required relatively drastic conditions. The 'drawbacks 'of such .methods include adverse effects on the Vpreferredsensitive catalysts of Vthe reduced nickel type conversion of the organic impurities to contaminants which'remain in the alcohol, conversion :of the alcohol to organic impurities which remain .in the alcohol, fand high expense of the treatment.

The present invention is "based on the discovery that improved practical results are obtained if .satisfactory conditions (temperature, pressure, and time) are uscdrin the catalytic hydrogenation N `First to enable use of satisfactory mild conditions, `the alcohol to be finished should be properly pretreated, preferably by an extractive distillation with water to Yeliminate all Vbut small or trace amounts of the contaminants which are to be finally reacted by the mild hydronishing.

alcohols finished by conventional (non-extractive) distillation are also subject to great improvement by the mild hydronishing technique. The overall elect of the mild hydrolinishing is principally in `improving `the odor and permanganate time, with little or no change in the content of miscellaneous organic impurities (M.O.I.). The hydrotinished product from conventional distillation generally have higher M.O.l. values than those from extractive distillation. More specifically this invention relates to the general effects of processing conditions to produce a final alcohol having excellent quality as measured in terms of odor, permanganate time and miscellaneous impurities.

The M.O.I. values are determined by optical density by which small variations inthe content and type of the miscellaneous organic impurities adequately show up. These values for ethanol to be hydronishe'd under satisfactory mild conditions are in the range of 0.015 to 1.0, preferably 0.015 to 0.1. Y

The highly sensitive M.O.I.. `test is carried `out by mixing the alcohol sample with salicylaldehyde and 98% sulfuric acid, 'heating the mixture until a yellow color is developed, then measuring the depth of the color with ultra violet spectrophotometer at a certain wave length, e.g. 550 mu. The M.O.I. value is reported as measured optical density. A low M.O.I. is required in a premium grade alcohol. g g

It should be noted thatv the alcohol feed suitable for the mild hydronishing of the present invention generally can be of widely variable quality with respect to odor and the -permanganate time test (P.T.). In general this test is a measure of small quantities of easily oxidized organic Figure l.

2,944,087. Patented July 5, 1950 impurities, the time being inversely proportional to the concentration of any given impurity. Good quality alcohols have permanganate times of at least 30-40 minutes.

For the P.T. test, 2 cc. of 0.2 g. KMnO., per liter 'aqueous solution are added to 50 cc. of the alcohol to be tested, and the time in minutes for the nose color of the mixture at 15 C. to disappear is determined.

it is 'preferable that the alcohol feed to hydrofinishing have a `permanganate time of not less than 20-30 minutes. As Vindicated by the examples to follow, this is increased to 50-'60 minutes. Such an alcohol is readily vobtained by the waterextractive ldistillation technique as described in the patent of Drout et al. UnS. 2,638,440, issued May "12, 1953.

The technique 'of this invention, however, is by no means limited to extractively distilled lfinished alcohols, but can include conventionally distilled alcohols having very low permanganate ytime (0-10 minutes), poor odors, and relatively high M.O.I. values. g

The odors `are measured by apanel of at least 3 members 'trained "in methods of odor evaluation. An odor rating of 2 is assigned to the standard of best odor quality alcohol available. 4Increasing values represent poorer odors 'up to scale l2. Alcohols of very poor odor are rated 12+. The odor is a very important consideration inthe case of commercial alcohols for certain specific uses. The so-ca'l'led `prime grades have odor ratings not greater than rclass 3. g

A llow plan of equipment used for preferred demonstration of the invention is shown in. the drawing Figure2 .of 'the `drawing shows grzmhically the effect of kleed rate on the M.O.I. values 'under suitable mild hydrogenation conditions. Figure. 3 showsthe effect lof temperature.

As shown in Figure 1, a crude ethanol `stream'from ethylene hydration is rst given a puritcation by water extractive distillation in tower 2. Sufficient water is introduced by line 3 atan upper part of tower 2 to give the internal aqueous reflux therein a water content above 65, and preferably to 99 mole percent. With suflicient heat input, under pressures of about l -to 5 atmospheres, the internal liquid reflux Aflowing down countercurrent to the vapors in tower 2 is maintained at temperatures above the boiling point of the aqueous alcohol (Le. above '80A C. and generally between and 100 C.) to cause impurities both lower and much higher boiling than the alcohol to distill overhead through line 4 with larger amounts of water vapor, more than present in aqueous azeotropes. The highly dilute `aqueous alcohol `freed of al1 but trace amounts of such impurities is withdrawn and passed by line 5 into rectifying column 6.

In rectifying column 6, the aqueous azeotrope of the alcohol ethanol with 5% water) is distilled to'be collected as an overhead product 'in receiver 7 or removed as an intermediate or side stream fraction 8. Residual Water and any high boiling impurities were removed from a lower 4part of column 6 as by line 9.

`.The rectiiied and concentrated liquid alcohol from column 6 can be passed directly to the mild hydroiinishing unit through lineyl. A pump ll and hea-t exchanger I2 in line l0 may be used for obtaining desired flow rates and temperatures in the `alcohol feed to the hydrogenation reactor '13.

Various active hydrogenation catalysts 'of the reduced nickel type such as Raney or supported nickel catalysts can be used for the hydroiinish'ing as in reactor 13'; The supported catalysts may Ybe onya support, 'such kieselguhr (Harshaw type). Similarly active catalysts of the platinum type may be used.

The feed of alcohol for hydrofimshing from line 10 4andjhydrogen from line 14 are mixed or introduced into the catalyst to form a well mixed liquid-gas mixture which is brought into contact with the solid catalyst. The hydrogen preferably contains less than 0.1% carbon monoxide. YThe conditions maintained in hydroiinishing reactor 13 determine the quality of the iinal product. Temperature and liquid feed rateY are the most critical variables: `temperatures are in the rangeV of 50-'160 F., preferably 65 -ll0 F. Liquid feed rates must be maintained above certain specific limits at any given temperature in order to prevent undesirable increases in M.O.I. values. The limits are here specifically dened in accordance with the examples to follow, but at the preferred temperatures of 65.110 F., the liquid feed rate should be not less than 2.5 volumes of feed per Volume of catalsyt per -hour and preferably about 5 volumes of feed per volume of catalyst per hour. Pressures very near atmospheric are suflicient to give the desired degree of product quality improvement.' Thus pressures in reactor 13 are in the range of 0-50 pounds/sq. inch gauge. The amount of hydrogen in proportion to the liquid feed is not too critical and is generally in the range of lv to-50 scf/barrel of feed. v

, T he Vgas and puriiied alcohot effluent from the reactor 13 is passed byl ine 15hinto a gas separator 16 to disengage and remove hydrogen by line 17. The-recovered H2 from line v17 may be recycledvto line 14. The hydrofinished alcohol is passed by` line 18 into a nal gas stripper or stabilizer 19. Heat exchanger 20 may be used in yvessel 19; for aidingA the stabilization. If desirable the gas separator may be omitted and the excess hydrogen removed from the stabilizer and recycled.

,Vapors taken overhead from column 19 through line VV`.21 `are cooled in condenser 22 to provide yreiux returned by line 23.v Uncondensed gaseous material is removed or-vented by line 24. Finished alcohol is collected'Y and withdrawn ras an intermediate fraction by line 25 or as Vbottom s withdrawn through line 26. Y

The qualities of various ethanol feed streams to hydrofinishing were compared. These Vfeeds are represented as follows:

TABLE I Conven- E. D. Prime E. D. Over tional head Odor, Class 8 to 12+...-- 4 to 10 12+ P.T-. 0 to 90 20 to 45. About 18 avg. M.O.I 0.2 to 1.0-... 0.02 to .l0-... 0.03 to 0.05

i v Oonventional=straight fractionation.

E.D. Prime=upper side stream from extractiva distillation rectifier. E.D. Overhead=overhead distillate extractiva distillation rectifier.

Example 1 Under the mild conditions (50 to 110 F. and 0 to 3 p.s.i.g.) the odor and P.T. of each type ethanol was markedly improved with no significant or appreciable change in the M.O.I. The maximum amount of hydrogen consumed in any run was 0.03 g. moles/ l. alcohol, but it was found unnecessary to use the maximum and some runs were stopped at about one-third the maximum. in obtaining `the improvement from class 12 vto acceptable class 2 odor with increase of P.T. up to 60 minutes from 20 minutes. yIn one-runhydrogen was not added and the quality of the alcohol wasY degraded evidently due to the formation of unsaturated components by decomposition of the alcohol.

Example 2 Under more drastic conditions (200 F. and 100-300 p.s.i.g.,; and 20G-350 'F., 1450-2000 p.s.i.g.) Harshaw nickel catalyst was used on typical production ethanols having P.T. values of 5 to 10 minutes. While in each run there was some improvement in odor and P.T. values of portions, a dependable over-all improvement was not obtained and the best improvement was obtained with the least drastic conditions (200 F., 100 p.s.i.g,) in which of intermediate (10%) cuts of the hydroiinished ethanol were of Grade l odor and with P.T. values of above 30.

Example 3 Milder conditions (temperatures in the range of 65 to 80 F. and pressures of .05-3 p.s.i.g.) were investigated in an attempt to find conditions under which the supported (Harshaw) nickel catalyst would not cause the undesirable increase in M.O.I. The experiments were carried out batchwise as were those described in Examples 1 and 2.

With the supported catalyst, the same maximum amount of hydrogen was finally consumed as with the unsupported Raney catalyst, but a considerably longer time was required. Odor was improved from Class 8-12 to Class 2, but P. T. was notimproved to the extent obtained with Raney nickel. M.O.I. was increased in every experiment in which the P.T. of alcohol was improved. Experiments made'varying the time of reaction indicated that the long contact time required to improve odor to the desired level was responsible for the increase in M.O.I. vAt shorter contact times up to 2.2 hours, the M.O.I. increased littleif any, but the odor was improved only from Class 8 to Class 4.

Example "41 TABLE II ETHANOLYDROFINISHING Y [76 F., 1 atm. pressure, 10-20 cu. itJbarrel electrolytic HL] Perman- Odor ganate M.O.I. Class Time,

Min. Y

Feed: 12+ 42 0.025

Flow Rate Products Y 7 v./v./hr 2- 5i 0. 058 2- 6l 0.025 23 v.lv./hr 2- 57 0.032 Feed: 6 to 8 42 0.025

Flow Rate Products- .v

-From a large number of experiments it was found possible to devise graphical relationship as shown in Figures 2 and 3 for ascertaining critical limits of flow rates and -hydroiinishing temperatures for satisfactory odor yand P.T. improvement .without undesirable excessive increase of miscellaneous organicimpurities in Vthe alcohol product. Thesev graphs show that the usually highest allowable increase of such impurities M.O.I. of

asians?? 3 ,7S is obtained if the liquid alcohol feed rate becomes less than 2.5 volumes per volume ofl catalyst per hour and if the hydronishing temperature rises to above 110 F.

Another factor of importance in using well selected low temperatures, is that the hydrogen used does not have to be extremely pure to prevent nickel carbonyl formation. Methanized hydrogen was successfully used in place of electrolytic hydrogen at temperatures below 110 F.

The data obtained in hydroiinishing at temperatures above 110 F., particularly at 160 and 170 F. indicates that the increase of M.O.I. to above 1.0 is caused by condensation reactions which are favored by contact time and temperature.

The data in Table ll shows that mild condition hydrofinishing assures products superior to the class 2 standard with improved P.T. and no appreciable adverse effects on M.O.I. The catalyst was used for 3 months without signs of activity loss. Highest selectivity for odor removal with least increase of M.O.l. was obtained at the higher feed rates of 5 to 23 v./v./hr. There was substantially no alcohol loss and extremely low hydrogen consumption (less than 0.5 s.c.f./b.).

Example 5 As shown in the following Table III there can be varations in the kind of odoriferous ethanol used as feed, but there is a point at which the mild hydrofinishing can not be used satisfactorily, i.e. When the alcohol is of the odor class much aboveV 12, a very low P.T., below 10, and an M.O.I. above 1.0. The feeds compared in Table III are:

FEED QUALITY AND SOURCE A. Extra prime grade--water extractive distillationrectifier side stream.

B. Prime grade-water extractive distillation-rectifer side stream.

C. High grade-water extractive distillation-rectier overhead.

D. Good regular grade-conventional fractionation.

The hydroiinished product was heated under total reflux to strip out dissolved hydrogen without loss of alcohol at 1 atm. and at 180 F. for about 15 minutes. The thus refluxed (stabilized) alcohol was cooled and analyzed.

TABLE IV M.O.I. P.T. Odor lank 0. 120 49 2 Stabilized (A) 0.023 59 2 nk (B 0.095 56 2 Stabilized (B) 0. 013 58 2 Blank (C)- 0. 128 56 2 Stabilized (C) 0. 014 58 2 All samples of hydrofinished alcohol on being stabilized showed good decrease of M.O.l. and some improvement of P.T.

Various modifications may be made in the system used for the hydrogenation of the alcohol. The liquid alcohol v E9 to be treated may be passed countercurrcnt `to the hydro gen gas when contacting the catalyst, such as reduced finely divided nickel or the like. y

An important step in the hydrofinishing operation is the stripping of dissolved hydrogen from the finished alcohol product. This step is important not only for preventing explosion during subsequent handling of the product but also for increasing the purity.l The hydrogen stripped from the alcohol may be used in the hydrogenation reactor. The stripping system shown in Fig. l may be used. In such a system one or two vessels may be used for stripping the dissolved hydrogen from the alcohol. Compared with processes which employ very high pressure there is a substantial advantage in using lowerpressure mild hydrogenation conditions which then permits stripping of dissolved hydrogen from the finished alcohol at close to atmospheric pressure.

The invention `described is claimed as follows:

l. A method of improving the quality of ethyl alcohol prepared by hydrating ethylene which comprises extractively distilling crude ethyl alcohol with water to produce an ethyl alcohol feed having a permanganate time test value of at least 20 minutes and a miscellaneous organic impurities ntunber of not more than about 0.1, contacting said ethyl alcohol with a reduced nickel catalyst at a temperature within the range of 65 to 110 F. and hydrogen pressure between about 0 to 50 p.s.i.g., at a feed rate of at least 5 volumes of alcohol feed per volume of cata lyst per hour, the contact time being below about 2.2 hours, fractionally distilling the thus hydronished alcohol to remove dissolved hydrogen therefrom and recovering an alcohol product having improved odor qualities, a higher permanganate time test value and a miscellaneous organic impurities concentration not greater than that of the ethyl alcohol feed.

2. The method of improving the quality of ethyl alcohol prepared by hydrating ethylene which comprises extractively distilling with water the ethyl alcohol formed by hydrating ethylene to produce a purified ethyl alcohol product having a permanganate time test value in the range of 20 to 45 minutes and a miscellaneous organic impurities number in the range of 0.015 to 0.1, contacting said purified ethyl alcohol product with a reduced nickel catalyst at a temperature in the range of 65 to 110 F. and with hydrogen under a pressure in the range of 0 to 50 psig., and purified ethanol being contacted at a feed rate not less than 2.5 volumes of liquid ethanol per volume of catalyst per hour, the contact time of the liquid ethyl alcohol with the catalyst being kept suiiiciently below 2.2 hours so that with improvement in the odor of the alcohol and increase of the permanganate time for the alcohol to within the range of 50 to 60 minutes while the maximum increase for the miscellaneous organic impurities number of the hydrogenated alcohol is kept below 0.075, and thereafter stabilizing the thus hydrofinished ethyl alcohol by fractional distillation under reflux to remove dissolved hydrogen therefrom.

3. A method of improving the quality of ethyl alcohol prepared by hydrating ethylene, which comprises extractively distilling with water the ethyl alcohol formed by hydrating ethylene to form a purified ethyl alcohol product having a permanganate time test value of at least 20 minutes and a miscellaneous organic impurities `number in the range of 0.015 to 0.1, contacting the thus purified ethyl alcohol product with a `reduced nickel catalyst at a temperature within the range of 65 to 110 F., under a hydrogen pressure in the range of 0 to 50 psig. and at a feed rate of not less than 2.5 volumes of liquid ethyl alcohol per volume of catalyst per hour until a maximum of hydrogen consumed amounts to 0.03 gram moles per liter of the alcohol, stopping further reaction of the hydrogen with an alcohol to prevent an increase of the miscellaneous organic impurities as the thus hy- -droiinished alcohol is given permanganate time in the .7 range of 50 to 60 minutes, and fractonally distillng the 2,525,354 'thus hydroinished alcohol to remove dissolved hydrogen 2,575,556 therefrom and recover an alcohol product of improved 2,726,199 qualities.

References Cited' in the tile of this patent 5 131 478 UNITED STATES PATENTS 153:306

Maycock et a1 May 27, 1952 8 Hoog et al. Oct. 10, 1950 Maycock et al Nov. 20, 1951 Biribauer et al Dec. 6, 1955 FOREIGN PATENTS Australia Feb. 22, 1949 Australia Sept. 22, 1953 Great Britain July 12,1950 

1. A METHOD OF IMPROVING THE QUALITY OF ETHYL ALCOHOL PREPARED BY HYDRATING ETHYLENE WHICH COMPRISES EXTRACTIVELY DISTILLING CRUDE ETHYL ALCOHOL WITH WATER TO PRODUCE AN ETHYL ALCOHOL FEED HAVING A PERMANGANATE TIME TEST VALUE OF AT LEAST 20 MINUTES AND A MISCELLANEOUS ORGANIC IMPURITIES NUMBER OF NOT MORE THAN ABOUT 0.1, CONTACTI NG SAID ETHYL ALCOHOL WITH A REDUCED NICKEL CATALYST AT A TEMPERATURE WITHIN THE RANGE OF 65* TO 110*F. AND HYDROGEN PRESSURE BETWEEN ABOUT 0 TO 50 P.S.I.G., AT A FEED RATE OF AT LEAST 5 VOLUMES OF ALCOHOL FEED PER VOLUME OF CATALYST PER HOUR, THE CONTACT TIME BEING VELOW ABOUT 2.2 HOURS, FRACTIONALLY DISTILLING THE THUS HYDROFINISHED ALCOHOL TO REMOVE DISSOLVED HYDROGEN THEREFROM AND RECOVERING AN ALCOHOL PRODUCT HAVING IMPROVED ODOR QUALITIES, A HIGHER PERMANGANATE TIME TEST VALUE AND A MISCELLANEOUS ORGANIC IMPURITIES CONCENTRATION NOT GREATER THAN THAT OF THE ETHYL ALCOHOL FEED. 